TWI757939B - Polycarbonate resin and method for preparing the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin and a method for preparing the same, and more specifically, to a polycarbonate resin which is prepared by interfacial polymerization of the polycarbonate oligomer obtained by melt polymerization with a ketone compound, and has excellent color, molding processability, heat resistance and impact resistance due to comprising repeating units derived from a carbonic acid diester component, an aromatic/aliphatic/alicyclic diol component and a ketone compound component, and a method for preparing the same.

Description

Polycarbonate resin and preparation method thereof

The present invention relates to a polycarbonate resin and a preparation method thereof, and more particularly, to a polycarbonate resin prepared by interfacial polymerization of a polycarbonate oligomer by melting with a ketone compound Obtained by polymerization, the polycarbonate resin has excellent color, molding processability, heat resistance and Impact resistance, and preparation method of the polycarbonate resin.

Aromatic bisphenol-based polycarbonates have excellent mechanical properties, such as tensile strength and impact resistance, and have excellent dimensional safety, heat resistance, and optical transparency, and thus are widely used for industrial purposes. Among them, polycarbonates derived from aromatic dihydroxy compounds, such as 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "bisphenol A"), are produced by two methods such as interfacial polymerization or melt polymerization. And industrialization. According to the interfacial polymerization method, polycarbonate can be prepared from bisphenol A and phosgene. However, since phosgene is toxic, its handling and handling is problematic. In addition, when using the interfacial polymerization method, chlorine-containing compounds such as hydrogen chloride and sodium chloride are by-produced, and a large amount of dichloride used as a solvent is used. Methane, as well as impurities (eg, sodium chloride, etc.), can corrode manufacturing equipment or make it difficult to remove residual methylene chloride that can affect polymer properties.

In another aspect, as a method for producing polycarbonate from an aromatic dihydroxy compound and diaryl carbonate, a melt polymerization method is known, for example, bisphenol A and diphenyl carbonate are transesterified in a molten state to polymerize Polycarbonate with removal of aromatic monohydroxy compounds (phenol in the case of bisphenol A and diphenyl carbonate) as by-products. Unlike the interfacial polymerization method, the advantage of the melt polymerization method is that it does not need to use a solvent, but as the polymerization progresses, the viscosity of the polymer in the system increases rapidly, and it is difficult to efficiently remove the aromatic monohydroxy compound from the system. And there is an important problem that it becomes difficult to increase the degree of polymerization due to an extremely low reaction rate. Therefore, there is a need for an efficient method for producing an aromatic polycarbonate resin having a high molecular weight by using a melt polymerization method.

As a method for solving the above-mentioned problems, for example, a method for producing a polycarbonate block copolymer (Korean Patent Registration No. 10-1608411 ) includes producing a polycarbonate oligomer containing isosorbide as a repeating unit using a melt polymerization method, and It is subjected to interfacial polymerization with a polycarbonate oligomer containing bisphenol A as a repeating unit. The problem, however, is that a high content of phosgene must still be used starting from the step of preparing the polycarbonate oligomer comprising bisphenol A as a repeating unit. When using this method, there is a limit to increasing the isosorbide content of the block copolymer.

Therefore, there is a need to develop a technology capable of producing polycarbonate resins excellent in all physical properties such as color, molding processability, heat resistance, and impact resistance, while reducing the amount of toxic phosgene used.

The object of the present invention is to provide a polycarbonate resin prepared by interfacial polymerization of a polycarbonate oligomer obtained by melt polymerization with a ketone compound, since it contains a component derived from carbonic acid diester , repeating units of an aromatic/aliphatic/alicyclic diol component and a ketone compound component, the polycarbonate resin having excellent color, molding processability, heat resistance and impact resistance, and preparation of the polycarbonate resin method.

In order to achieve the technical purpose, in a first aspect, the present invention provides a polycarbonate resin comprising a repeating unit derived from a carbonic acid diester component represented by the following formula 1; a repeating unit derived from a diol component represented by the following formula 2 unit; and a repeating unit derived from a ketone compound component represented by the following formula 3, wherein the polycarbonate resin contains a carbonic diester component and a ketone compound component in a molar ratio of 1:0.02 to 1:0.2:

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms aralkyl,

[Formula 2] HO-X-OH

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight chain alkylene group having 1 to 15 carbon atoms; a branched chain alkylene group having 3 to 15 carbon atoms ; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohols, and Aryl, straight-chain, branched, and cyclic alkylene groups may be unsubstituted or substituted with halogen atoms, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, nitro or carboxyl substitution, and

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; or unsubstituted or substituted with O, N or An aryl group having 3 to 50 carbon atoms is substituted by Cl, and it is excluded that both R ₂ and R ₃ are halogen atoms.

In another aspect, the present invention provides a method for producing a polycarbonate resin, comprising (1) derivatizing a repeating unit derived from a carbonic acid diester component represented by the following formula 1 and a diol component represented by the following formula 2 and (2) by combining the prepared hydroxyl-terminated polycarbonate oligomer with the following The step of preparing the polycarbonate resin by interfacial polymerization of the ketone compound component represented by the formula 3, wherein the reaction molar ratio of the carbonic acid diester component represented by the following formula 1 and the ketone compound component represented by the following formula 3 is 1: 0.02 to 1:0.2:

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms aralkyl,

[Formula 2] HO-X-OH

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight chain alkylene group having 1 to 15 carbon atoms; a branched chain alkylene group having 3 to 15 carbon atoms ; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohols, and an arylene group, a straight-chain alkylene group, a branched-chain alkylene group, and a cyclic alkylene group may be unsubstituted or substituted with halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryl groups, nitro groups or carboxyl groups, and

In formula 3, R ₂ and R ₃ are each independently a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; or unsubstituted or substituted with O, N or an aryl group having 3 to 50 carbon atoms substituted by Cl, excluding that _both R and _R are halogen atoms, and

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

In another aspect, the present invention provides a molded article comprising the above-described polycarbonate resin.

Since the polycarbonate resin according to the present invention is excellent in various physical properties such as color, heat resistance and impact resistance, it can be very suitable for molded articles such as those for electrical/electronic parts such as televisions and mobile phones. materials, and materials used in automotive parts such as lamps and lenses. In addition, the preparation method according to the present invention has an advantage in that, compared with the conventional polycarbonate manufacturing technology, it can produce environmentally friendly polycarbonate by using less phosgene and solvent, and at the same time by easily The molecular weight is adjusted to prepare high molecular weight polycarbonate resins.

As used herein, the term "reaction product" refers to a material formed by reacting two or more reactants.

In addition, in this specification, terms such as "first" and "second" are used to describe the polymerization catalyst, but the polymerization catalyst is not limited by these terms. These terms are only used to distinguish polymerization catalysts. For example, the first polymerization catalyst and the second polymerization catalyst can be the same type or different types of catalysts.

In addition, the English letter "R" used to represent hydrogen, a halogen atom and/or a hydrocarbon group in the formula described in this specification has a subscript represented by a number, but "R" is not limited to this subscript. The above-mentioned "R" independently represents hydrogen, a halogen atom, and/or a hydrocarbon group or the like. For example, whether two or more "Rs" have the same or different numbers of subscripts, these "Rs" can represent the same or different hydrocarbyl groups.

The present invention is explained in more detail below.

The polycarbonate resin of the present invention comprises a repeating unit derived from a carbonic acid diester component represented by the following formula 1; a repeating unit derived from a diol component represented by the following formula 2; and a ketone compound represented by the following formula 3 A repeating unit derived from a component, wherein the polycarbonate resin comprises a carbonic diester component and a ketone component in a molar ratio of 1:0.02 to 1:0.2:

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms aralkyl,

[Formula 2] HO-X-OH

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight chain alkylene group having 1 to 15 carbon atoms; a branched chain alkylene group having 3 to 15 carbon atoms ; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohols, and an arylene group, a straight-chain alkylene group, a branched-chain alkylene group, and a cyclic alkylene group may be unsubstituted or substituted with halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryl groups, nitro groups or carboxyl groups, and

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; or unsubstituted or substituted with O, N or Cl-substituted aryl groups having 3 to 50 carbon atoms, excluding that both R ₂ and R ₃ are halogen atoms.

Regarding the molar ratio of the carbonic diester component and the ketone compound component, when the molar ratio of the carbonic diester component is 1, the molar ratio of the ketone compound component may be 0.02 or more, 0.04 or more, 0.05 or more, 0.08 or more above or 0.1 or above, and 0.2 or below, 0.18 or below, 0.16 or below, 0.15 or below, 0.12 or below, or 0.1 or below, for example may be 1:0.02 to 1:0.2, 1:0.04 to 1:0.18 or 1:0.05 to 1:0.15. If the molar ratio of the carbonic acid diester component and the ketone compound component is less than the above range, the reactivity decreases and the viscosity average molecular weight of the polycarbonate resin decreases, resulting in poor impact resistance and color. On the other hand, if the molar ratio is larger than the above range, the viscosity-average molecular weight of the polycarbonate resin may increase excessively, which may result in poor processability and color.

The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is 10,000 to 70,000, preferably 15,000 to 50,000, and more preferably 15,000 to 30,000. if With a viscosity average molecular weight of less than 10,000, there is a problem in achieving sufficient mechanical properties. If the viscosity average molecular weight exceeds 70,000, the molecular weight is too high, the meltability is poor, and processing is difficult.

In one embodiment, the carbonic acid diester component represented by Formula 1 may be selected from diphenyl carbonate, dichlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate or mixtures thereof, and more Preferably, diphenyl carbonate or dimethyl carbonate can be used.

In one embodiment, in Formula 2, the halogen atom may be F, Cl or Br, and the alkyl group may be an alkyl group having 1 to 20 carbon atoms (more specifically, having 1 to 13 carbon atoms) atoms, such as methyl, ethyl, propyl, or butyl), the cycloalkyl group may be a cycloalkyl group having 3 to 10 carbon atoms (more specifically, a cycloalkyl group having 3 to 6 carbon atoms) cycloalkyl), the alkenyl group may be an alkenyl group having 2 to 20 carbon atoms (more specifically, it may be an alkenyl group having 2 to 13 carbon atoms), and the alkoxy group may be an alkenyl group having 1 An alkoxy group having to 20 carbon atoms (more specifically, an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy, propoxy or butoxy) and the aryl group may be An aryl group having 6 to 30 carbon atoms (more specifically, an aryl group having 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl or naphthyl).

In one embodiment, the diol component represented by Formula 2 may be an aromatic diol, an aliphatic diol, an alicyclic diol, an anhydrosugar alcohol, or a mixture thereof.

As the aromatic diol, for example, unsubstituted or substituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, a nitro group or a carboxyl group can be used (for example, bisphenol A, bisphenol A, bisphenol A, bisphenol A, bisphenol A, bisphenol A, bisphenol A, bisphenol A, phenol F, bisphenol TMC, etc.), resorcinol, hydroquinone, biphenol, naphthalenediol or mixtures thereof, preferably unsubstituted or via halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, Alkoxy, aryl, nitro or carboxyl substituted bisphenol A.

The aliphatic diol may be, for example, an aliphatic diol having 2 to 10 carbon atoms, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propanediol, 1,3- Propylene glycol, etc.), butanediol (1,2-butanediol, 1,3-butanediol, 1,4-butanediol, etc.), pentanediol (1,2-pentanediol, 1,3-butanediol, etc.) pentanediol, 1,4-pentanediol, 1,5-pentanediol, etc.), hexanediol (1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, etc.), neopentyl glycol or mixtures thereof, preferably butanediol, unsubstituted or substituted by halogen atoms, alkyl groups, cycloalkyl groups, alkenes group, alkoxy group, aryl group, nitro group or substituted with carboxyl group.

The alicyclic diol may be, for example, cyclohexanediol (1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, etc.), cyclohexanediol Alkanedimethanol (1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, etc.), tetramethylcyclobutanediol or mixtures thereof, preferably Cyclohexanediols, unsubstituted or substituted with halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryl groups, nitro groups or substituted with carboxyl groups.

As the anhydrosugar alcohol, a dianhydrosugar hexitol can be used, for example, isosorbide, isomannide, isoidide or a mixture thereof can be used, and preferably isosorbide can be used .

In one embodiment, in Formula 2, X may be an arylene group, which may be derived from a substituted or unsubstituted bisphenol (eg, bisphenol A, bisphenol F, or bisphenol TMC, etc.), a Substituted or unsubstituted resorcinol, substituted or unsubstituted hydroquinone (such as hydroquinone, 2-nitrohydroquinone, 2-sulfonylhydroquinone, etc.), A substituted or unsubstituted biphenol, a substituted or unsubstituted naphthalenediol, or a substituted or unsubstituted diphenol—for example, it may be represented by the following formulae 2a to 2h.

[Formula 2c]

In one embodiment, in Formula 2, X can be a ethylene glycol that can be derived from substituted or unsubstituted ethylene glycol, substituted or unsubstituted propylene glycol, or substituted or unsubstituted butanediol Alkyl - For example, it can be ethylene, propylene or butylene.

In one embodiment, in Formula 2, X can be a cycloalkylene group, which can be derived from substituted or unsubstituted cyclohexanediol, substituted or unsubstituted cyclohexanedimethanol, or Substituted or unsubstituted tetramethylcyclobutanediol - for example, it can be represented by the following formulae 2i to 2k.

In one embodiment, in Formula 2, X may be a divalent organic group derived from an anhydrosugar alcohol - for example, it may be represented by Formulas 21 to 2n below.

In one embodiment, in addition to phosgene (ie, when R ₂ and R ₃ in Formula 3 are both halogen atoms), the ketone compound component represented by Formula 3 may be selected from compounds represented by the following Formulae 3a to 3d .

In another aspect, the present invention provides a method for producing a polycarbonate resin, comprising (1) derivatizing a repeating unit derived from a carbonic acid diester component represented by the following formula 1 and a diol component represented by the following formula 2 and (2) by combining the prepared hydroxyl-terminated polycarbonate oligomer with the following The step of preparing the polycarbonate resin by interfacial polymerization of the ketone compound component represented by the formula 3, wherein the reaction molar ratio of the carbonic acid diester component represented by the following formula 1 and the ketone compound component represented by the following formula 3 is 1: 0.02 to 1:0.2:

[Formula 1]

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms aralkyl,

[Formula 2] HO-X-OH

In Formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight chain alkylene group having 1 to 15 carbon atoms; a branched chain alkylene group having 3 to 15 carbon atoms ; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohols, and an arylene group, a straight-chain alkylene group, a branched-chain alkylene group, and a cyclic alkylene group may be unsubstituted or substituted with halogen atoms, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, nitro or carboxyl groups,

In Formula 3, R ₂ and R ₃ are each independently a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; or unsubstituted or substituted with O, N or an aryl group having 3 to 50 carbon atoms substituted by Cl, excluding that _both R and _R are halogen atoms, and

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

(A) Preparation of hydroxyl terminated polycarbonate oligomers (melt polymerization)

The method for producing a polycarbonate resin of the present invention includes (1) a repeating unit derived from a carbonic acid diester component represented by the following formula 1 and a repeat unit derived from a diol component represented by the following formula 2 A step of preparing a hydroxyl-terminated polycarbonate oligomer having a unit structure represented by the following formula 4 by melt-polymerizing multiple units.

The carbonic acid diester component represented by Formula 1 and the diol component represented by Formula 2 used in the production method of the present invention are as described above in the polycarbonate resin part.

The hydroxyl-terminated polycarbonate oligomer constituting the repeating unit of the polycarbonate resin of the present invention has a unit structure represented by the following formula 4.

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100.

The hydroxyl-terminated polycarbonate oligomer having the unit structure represented by Formula 4 may have a viscosity average molecular weight (Mv) of 1,000 to 20,000, and more preferably 5,000 to 15,000.

If the viscosity average molecular weight of the hydroxyl terminated polycarbonate oligomer is less than 1,000, the effect of reducing the amount of toxic phosgene or its substitute material in the interfacial polymerization step may not be significant. If the viscosity average molecular weight exceeds 20,000, it is difficult to synthesize a polycarbonate resin having a desired molecular weight due to a decrease in reactivity in the interfacial polymerization step.

The hydroxyl-terminated polycarbonate oligomer having the unit structure represented by the formula 4 can be obtained by combining the carbonic acid diester component represented by the above formula 1 with the diol component represented by the above formula 2 (for example, aromatic diol, aliphatic Diols, alicyclic diols, anhydrosugar alcohols or mixtures thereof) are prepared by melt polymerization.

The carbonate diester component and the diol component are as described above in the polycarbonate resin section.

The amount of the carbonic diester component is preferably 0.8 to 1.2 mol per 1 mol of the diol component. If the amount of the carbonic diester component exceeds 1.02 mol per 1 mol of the diol component, it may be difficult to obtain a sufficient molecular weight since the carbonate residue acts as a terminal terminator of hydroxyl terminated polycarbonate oligomers. If the amount of the carbonate diester component is less than 0.8 mol per 1 mol of the diol component, the diol component acts as a terminal terminator, and thus it may be difficult to obtain a hydroxyl-terminated polycarbonate oligomer having a sufficient molecular weight.

The carbonate diester component and the diol component can be melt-polymerized in the presence of a polymerization catalyst.

As the polymerization catalyst, alkali metal salt compounds (such as sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, cesium carbonate, etc.); alkaline earth metal salt compounds (such as calcium hydroxide, barium oxide, magnesium oxide, etc.) can be used etc.); nitrogen-containing basic compounds (eg, tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine, etc.) or mixtures thereof, etc., which may be used alone or in combination of two or more. Among them, a nitrogen-containing basic compound and an alkali metal salt compound are more preferably used in combination.

The amount of the polymerization catalyst is preferably 1 × 10 ^-9 to 1 × 10 ^-3 mol equivalent, more preferably 1 × 10 ^-8 to 5 × 10 ^-4 mol equivalent per 1 mol of carbonic diester .

The melt polymerization can be carried out under high temperature conditions, eg, 180°C to 240°C (more specifically, 200°C to 220°C), and under normal pressure or reduced pressure (eg, 0.1 torr to 50 torr).

According to one embodiment of the present invention, the melt polymerization can be performed by including mixing the carbonic acid diester component represented by Formula 1, the diol component represented by Formula 2 and the polymerization catalyst, and increasing the temperature to 180°C to 240°C (eg, 200° C.) followed by the step of reacting the mixture; and reacting the mixture at a temperature of 180° C. to 240° C. under a reduced pressure of 50 torr or less (eg, 0.1 torr to 50 torr) to remove alcohol as a side reactant ( For example, phenol or methanol, etc.) can be carried out.

(B) Preparation of polycarbonate resin (interfacial polymerization)

The polycarbonate resin of the present invention contains repeating units derived from the ketone compound component represented by the above formula 3.

The production method of the present invention includes a step of producing a polycarbonate resin by interfacial polymerization of the produced hydroxyl-terminated polycarbonate oligomer with the ketone compound component represented by the above formula 3.

The ketone compound component represented by Formula 3 is as described in the polycarbonate resin section.

In the production method of the present invention, the carbonic acid diester component represented by the above formula 1 and the ketone compound component represented by the above formula 3 may be used in a molar ratio of 1:0.02 to 1:0.2.

Regarding the molar ratio of the carbonic diester component and the ketone compound component, when the molar ratio of the carbonic diester component is 1, the molar ratio of the ketone compound component may be 0.02 or more, 0.04 or more, 0.05 or more, 0.08 or more above or 0.1 or above, and 0.2 or below, 0.18 or below, 0.16 or below, 0.15 or below, 0.12 or below, or 0.1 or below, for example may be 1:0.02 to 1:0.2, 1:0.04 to 1:0.18 or 1:0.05 to 1:0.15. If the molar ratio of the carbonic acid diester component and the ketone compound component is less than the above range, the reactivity decreases and the viscosity average molecular weight of the polycarbonate resin decreases, resulting in poor impact resistance and color. On the other hand, if the molar ratio is larger than the above range, the viscosity-average molecular weight of the polycarbonate resin may increase excessively, which may result in poor processability and color.

The interfacial polymerization reaction can be carried out under interfacial reaction conditions consisting of an aqueous alkali solution and an organic phase.

For the interfacial polymerization reaction, a hydroxyl-terminated polycarbonate oligomer having a unit structure represented by the above formula 4 and a ketone compound component represented by the above formula 3 may be added to a reactor, and a molecular weight adjustment may be additionally thereto. A reagent, a first polymerization catalyst, a phase transfer catalyst, and a pH adjuster (eg, NaOH), methylene chloride (MC), etc. are added to the reactor. Specifically, the polycarbonate resin can be prepared by adding a ketone compound component to an organic phase-aqueous phase mixture containing a hydroxyl-terminated polycarbonate oligomer and adding a molecular weight modifier, a catalyst, and the like thereto in stages.

As molecular weight regulators, monofunctional compounds similar to those used for the production of polycarbonates can be used. The monofunctional compound may be, for example, a phenol-based derivative such as p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, p-isononylphenol, etc.; or a fatty acid Alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

As the catalyst, a polymerization catalyst and/or a phase transfer catalyst can be used. As the polymerization catalyst, for example, triethylamine (TEA) can be used, and as the phase transfer catalyst, for example, a compound represented by the following formula 5 can be used.

[Formula 5] (R ₄ ) ₄ Q ⁺ Y ⁻

In Formula 5, R ₄ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Y represents a halogen atom or -OR ₅ , wherein R ₅ represents a hydrogen atom, a carbon atom having 1 to 18 carbon atoms Alkyl or aryl having 6 to 18 carbon atoms.

Specifically, the phase transfer catalyst may be, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NY, [CH ₃ (CH ₂ ) ₃ ] ₄ PY, [CH ₃ (CH ₂ ) ₅ ] ₄ NY, [CH ₃ (CH 2 ) 5 ] 4 NY, [CH 3 (CH 2 ) 3 ] 4 PY ₂ ) ₆ ] ₄ NY, [CH ₃ (CH ₂ ) ₄ ] ₄ NY, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NY, or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NY. In the above formula, Y represents Cl, Br or -OR ₅ , wherein R ₅ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10 wt %, and more preferably 0.1 to 10 wt %, based on the total weight of the hydroxyl terminated polycarbonate oligomer. If the content is less than 0.01% by weight, the reactivity may decrease. If the content is more than 10% by weight, the phase transfer catalyst may precipitate, or the transparency of the polycarbonate resin may decrease.

In a preferred embodiment, the interfacial polymerization of the hydroxyl-terminated polycarbonate oligomer and the ketone compound components may be performed stepwise in the first and second steps. Specifically, the first polymerization step can be carried out from the following mixture: hydroxyl terminated polycarbonate oligomer, ketone compound Chemical components, a first polymerization catalyst, a phase transfer catalyst, a molecular weight regulator, a pH regulator (eg, NaOH), dichloromethane (MC), and the like are added thereto. Then, the second polymerization step can be carried out by sequentially adding a second polymerization catalyst thereto. After the first polymerization step is completed, the second polymerization step can be carried out by providing a second polymerization catalyst to the resulting mixture.

In one embodiment, the polymer is prepared by the melt polymerization step and the interfacial polymerization step as described above, and then the organic phase dispersed in dichloromethane is washed with alkali and separated. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then 2 to 3 times with distilled water. When the washing is complete, the concentration of the organic phase dispersed in dichloromethane is continuously adjusted and granulated using a certain amount of distilled water in the range of 30°C to 100°C, preferably 60°C to 80°C . If the temperature of the distilled water is lower than 30°C, the granulation speed may be slow and the granulation time may be long. If the temperature of the distilled water exceeds 100°C, it may be difficult to obtain the shape of the polycarbonate of constant size. After the granulation is completed, it is preferably dried at 100°C to 120°C for 5 to 10 hours, more preferably first dried at 100°C to 110°C for 5 to 10 hours, and then dried at 110°C to 120°C for 5 to 10 hours .

Since the polycarbonate resin according to the present invention is excellent in various physical properties such as color, heat resistance and impact resistance, it can be very suitable for molded articles such as electrical/electronic applications such as televisions and mobile phones Materials for parts and for automotive parts such as lamps and lenses.

Accordingly, in another aspect, the present invention provides a molded article comprising the polycarbonate resin of the present invention.

The method of molding the polycarbonate resin of the present invention into a molded article is not particularly limited, and a molded article can be produced by a method generally used in the field of plastic molding.

The present invention is explained in more detail by the following examples and comparative examples. However, the scope of the present invention is not limited in any way.

[Example]

Example 1

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

275 g (1.2 mol) of bisphenol A, 215 g (1 mol) of diphenyl carbonate, and 0.0001 g of cesium carbonate were added to a 2L three-neck reactor, and slowly stirred under nitrogen atmosphere and the temperature was raised to 200 °C. The pressure was gradually reduced to 0.1 torr over 90 minutes, and the temperature was raised to 220 °C under reduced pressure to remove the side reactant phenol. After that, the pressure reduction was resumed, and 240 g (0.16 mol) of a hydroxyl-terminated aromatic polycarbonate oligomer represented by the following formula 6 having a number average molecular weight (Mn) of 1,510 was obtained.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

In a 2L three-neck reactor, mix 240g polycarbonate oligomer obtained in step 1, 16g (0.05mol) triphosgene of formula 3b, 350g 5wt% aqueous sodium hydroxide solution, 1L dichloromethane, 1g ( 0.007 mol) p-tert-butylphenol (PTBP) and 250 μL of a 15 wt % trimethylamine (TEA) aqueous solution, and then reacted for 60 minutes. For the reaction results, 0.3 L of dichloromethane and 300 μL of a 15 wt % triethylamine aqueous solution were mixed, and then reacted for an additional 1 hour.

After separation of the layers, the viscosity-increasing organic phase was washed with alkali and separated. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution and then repeated 2 to 3 times with distilled water. After washing, the organic phase was granulated at 76°C using a certain amount of distilled water. After the granulation was completed, it was first dried at 110° C. for 8 hours, and then dried at 120° C. for 10 hours to prepare a high molecular weight polycarbonate resin. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Example 2

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

Prepared in the same manner as in Example 1, except that the reaction time under reduced pressure was changed from 90 minutes to 60 minutes to remove the side reactant phenol, 235 g (0.32 mol) of formula 7 having a number average molecular weight (Mn) of 740 Hydroxyl terminated aromatic polycarbonate oligomers.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

A high molecular weight polycarbonate resin was prepared in the same manner as described in Example 1, except that 235 g (0.32 mol) of the polycarbonate oligomer of formula 7 obtained in Step 1 was used instead of 240 g (0.16 mol) in Example 1 In addition to the polycarbonate oligomer of Formula 6 obtained in , the content of triphosgene of Formula 3b was changed. From 16 g (0.05 mol) to 33 g (0.11 mol), and changing the content of 5 wt % aqueous sodium hydroxide solution from 350 g to 700 g. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Example 3

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of the hydroxyl-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

A high molecular weight polycarbonate resin was prepared in the same manner as described in Example 1, except that 26 g (0.16 mol) of carbonyldiimidazole of formula 3c was used instead of 16 g (0.05 mol) of triphosgene of formula 3b. The physical properties of the carbonate resins are described in Table 1 below.

Example 4

<Step 1: Preparation of Isosorbide Polycarbonate Oligomer>

The reaction time under reduced pressure was changed from 90 min to 120 min to remove the side reactant phenol 220 g (0.21 mol), with the exception of using 177 g (1.2 mol) of isosorbide instead of 275 g (1.2 mol) of bisphenol A A hydroxyl-terminated aliphatic polycarbonate oligomer having a number average molecular weight (Mn) of 1,050 represented by the following formula 8 was obtained in the same manner as in Example 1.

<Step 2: Preparation of High Molecular Weight Isosorbide Polycarbonate Resin>

A high molecular weight polycarbonate resin was prepared in the same manner as described in Example 1, except that 220 g (0.21 mol) of the polycarbonate oligomer of formula 8 obtained in Step 1 was used instead of 240 g (0.16 mol) in Example 1 Polycarbonate oligomers of formula 6 obtained in and using 33 g (0.2 mol) of carbonyldiimidazole of formula 3c instead of 16 g (0.05 mol) of triphosgene of formula 3b, and changing the content of 5 wt % aqueous sodium hydroxide solution from 350g was changed to 550g, and the physical properties of the prepared polycarbonate resin were measured and described in Table 1 below.

Example 5

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer and Isosorbide Polycarbonate Oligomer>

138 g (0.6 mol) of bisphenol A, 108 g (0.5 mol) of diphenyl carbonate, and 0.00005 g of cesium carbonate were added to a 2L three-neck reactor, and the reactor was slowed down under nitrogen atmosphere. The temperature was raised to 200°C with slow stirring. The pressure was gradually reduced to 0.1 torr over 90 minutes, and the temperature was raised to 220°C under reduced pressure to remove the side reactant phenol. After that, the pressure reduction was resumed, and 117 g (0.08 mol) of a hydroxyl-terminated aromatic polycarbonate oligomer represented by the following formula 6 having a number average molecular weight (Mn) of 1,530 was obtained.

In addition, 89 g (0.6 mol) of isosorbide, 108 g (0.5 mol) of diphenyl carbonate, and 0.00005 g of cesium carbonate were added to a 2L three-neck reactor, and the temperature was increased under nitrogen atmosphere with slow stirring. Raised to 200°C. The pressure was gradually reduced to 0.1 torr over 120 minutes, and the temperature was raised to 220°C under reduced pressure to remove the side reactant phenol. After that, the pressure reduction was resumed, and 105 g (0.1 mol) of a hydroxyl-terminated aliphatic polycarbonate oligomer represented by the following formula 8 having a number average molecular weight (Mn) of 1,020 was obtained.

<Step 2: Preparation of High Molecular Weight Polyisosorbide Carbonate-Bisphenol A Carbonate Copolymer Resin>

In a 2L three-neck reactor, mix 105g of bisphenol A polycarbonate oligomer of formula 6 and 105g of isosorbide polycarbonate oligomer of formula 8 obtained in step 1, 16g (0.05mol) of formula 3b Sanguang gas, 350 g of 5 wt % aqueous sodium hydroxide solution, 1 L of dichloromethane, 1 g (0.007 mol) of p-tert-butylphenol (PTBP) and 250 μL of 15 wt % aqueous triethylamine solution were reacted for 60 minutes. For the reaction results, 0.3 L of dichloromethane and 300 μL of a 15 wt % triethylamine aqueous solution were mixed, and then reacted for an additional 1 hour.

After separation of the layers, the viscosity-increasing organic phase was washed with alkali and separated. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution and then repeated 2 to 3 times with distilled water. After washing, the organic phase was granulated at 76°C using a certain amount of distilled water. After the granulation was completed, it was first dried at 110° C. for 8 hours, and then dried at 120° C. for 10 hours to prepare a high molecular weight poly(isosorbide carbonate-bisphenol A carbonate) copolymer resin. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Comparative Example 1

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

230g (1mol) of bisphenol A, 240g of 33wt% sodium hydroxide aqueous solution, 100g (0.34mol) of triphosgene and 1L of dichloromethane were added to a 2L three-neck reactor, and reacted at room temperature for 30 minutes to obtain 250 g (0.17 mol) of the hydroxyl-terminated aromatic polycarbonate oligomer of formula 6 above had a dissolved number average molecular weight (Mn) of 1,480 in 1.3 kg of dichloromethane.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

In a 2L three-neck reactor, the resulting polycarbonate oligomer solution, 1.2 g (0.008 mol) of p-tert-butylphenol (PTBP) and 250 μL of a 15 wt % triethylamine aqueous solution were mixed, and then reacted for 60 minutes. For the reaction result, 360 g of dichloromethane and 300 μL of a 15 wt % triethylamine aqueous solution were mixed, and then reacted for an additional 30 minutes.

After separation of the layers, the viscosity-increasing organic phase was washed with alkali and separated. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution and then repeated 2 to 3 times with distilled water. After washing, the organic phase was granulated at 76°C using a certain amount of distilled water. After the granulation was completed, it was first dried at 110° C. for 8 hours, and then dried at 120° C. for 10 hours to prepare a high molecular weight polycarbonate resin. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Comparative Example 2

251 g (1.1 mol) of bisphenol A, 215 g (1 mol) of diphenyl carbonate, and 0.0001 g of cesium carbonate were added to a 2L three-neck reactor, and the temperature was raised to 200 °C while stirring slowly in a nitrogen atmosphere. °C. The pressure was gradually decreased to 0.1 torr over 180 minutes, and the temperature was increased to 240° C. under reduced pressure to remove the side reactant phenol, thereby preparing a high molecular weight aromatic polycarbonate resin. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Comparative Example 3

Same as Comparative Example 2 except that 177 g (1.2 mol) of isosorbide was used instead of 251 g (1.1 mol) of bisphenol A and the reaction time under reduced pressure was changed from 180 minutes to 200 minutes to remove the side reactant phenol way to prepare high molecular weight aliphatic polycarbonate resin. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Comparative Example 4

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of the hydroxyl-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

A high molecular weight polycarbonate resin was prepared in the same manner as in Example 1, except that the content of triphosgene of Formula 3b was changed from 16 g (0.05 mol) to 70 g (0.22 mol). The polycarbonate resins were measured and described in Table 1 below.

Comparative Example 5

<Step 1: Preparation of Bisphenol A Polycarbonate Oligomer>

In the same manner as in Example 1, 240 g (0.16 mol) of the hydroxyl-terminated aromatic polycarbonate oligomer of Formula 6 was obtained.

<Step 2: Preparation of High Molecular Weight Bisphenol A Polycarbonate Resin>

A high molecular weight polycarbonate resin was prepared in the same manner as in Example 1, except that the content of triphosgene of Formula 3b was changed from 16 g (0.05 mol) to 3.2 g (0.01 mol). The polycarbonate resins were measured and described in Table 1 below.

Comparative Example 6

<Preparation of hydroxyl-terminated isosorbide carbonate-aromatic carbonate oligomers and bisphenol A polycarbonate oligomers>

238 g (1 mol) of diphenyl carbonate, 155 g (1.1 mol) of isosorbide, and 0.0001 g of cesium carbonate were added to a 2L three-neck condensation reactor, and the temperature was raised to 200°C. The pressure was gradually reduced to 0.1 torr for 1 hour to remove phenol as a side reaction product under reduced pressure. After that, the reduced pressure was restored, and 25 g (0.1 mol) of bisphenol A was additionally added, followed by reducing the pressure to 0.1 torr at 220° C. and reacting under reduced pressure for 30 minutes. As a result, a hydroxyl-terminated (isosorbate carbonate-aromatic carbonate) oligomer represented by the following formula 9 was obtained.

In addition, 230 g (1 mol) of bisphenol A, 240 g of 33 wt % aqueous sodium hydroxide solution, 100 g (0.34 mol) of triphosgene and 1 L of dichloromethane were added to 2 L of three-necked reactor and react at 90 °C. It was left at room temperature for 30 minutes to obtain 250 g (0.17 mol) of a hydroxyl-terminated aromatic polycarbonate oligomer of the following formula 6 having a number average molecular weight (Mn) of 1,480 in a dissolved state in 1.3 Kg of dichloromethane.

<Preparation of High Molecular Weight Polyisosorbide Carbonate-Bisphenol A Carbonate Copolymer>

In a 2L three-neck reactor, 250 g of the bisphenol A polycarbonate oligomer of the above formula 6 was dissolved in dichloromethane, and 50 g of the hydroxyl terminated (isosorbate carbonate-aromatic carbonic acid of the above formula 9) ester) hydroxyl oligomer (based on 100% by weight of the bisphenol A polycarbonate oligomer of formula 6, corresponding to a content of 20% by weight) in dichloromethane, 1.2 g (0.008 mol) of p-tert-butyl Phenol (PTBP) and 250 μL of a 15 wt% triethylamine aqueous solution were mixed, and then reacted for 60 minutes. For the reaction result, 360 g of dichloromethane and 300 μL of a 15 wt % triethylamine aqueous solution were mixed, and then reacted for an additional 30 minutes.

After separation of the layers, the viscosity-increasing organic phase was washed with alkali and separated. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution and then repeated 2 to 3 times with distilled water. After washing, the organic phase was granulated at 76°C using a certain amount of distilled water. After the granulation was completed, it was first dried at 110°C for 8 hours, and then dried at 120°C for 10 hours to prepare [poly(isosorbide carbonate-bisphenol A carbonate)]-[polycarbonate] block copolymer . The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

Comparative Example 7

<Preparation of hydroxyl-terminated isosorbide carbonate-aromatic carbonate oligomers and bisphenol A polycarbonate oligomers>

In the same manner as in Comparative Example 6, a hydroxyl-terminated (isosorbate carbonate-bisphenol A carbonate) oligomer of formula 9 was obtained, and in the state of being dissolved in 1.3 Kg of dichloromethane, obtained and compared Example 6 The same 250 g (0.17 mol) of the hydroxyl terminated aromatic polycarbonate oligomer of formula 6.

<Preparation of High Molecular Weight Polyisosorbide Carbonate-Bisphenol A Carbonate Copolymer>

In addition to changing the content of the hydroxyl terminated (isosorbate carbonate-aromatic carbonate) oligomer of formula 9 from 50 g (based on 100 wt % of the bisphenol A polycarbonate oligomer of formula 6, corresponding to 20 wt % [poly(isosorbide carbonate)] was prepared in the same manner as in Comparative Example 6, except that the content of the - bisphenol A carbonate)]-[polycarbonate] block copolymer. The physical properties of the prepared polycarbonate resins were measured and described in Table 1 below.

<Method of Measuring Physical Properties>

(a) Viscosity-average molecular weight (Mv): The viscosity of the dichloromethane solution was measured at 20°C using an Ubbelohde viscometer, and the intrinsic viscosity [η] was calculated by the following equation:

[η]=1.23x10 ^-5 Mv ^0.83

(b) Impact strength: According to ASTM D256, notch-cut samples were prepared from the polycarbonate resins of each of the Examples and Comparative Examples, and the impact strength of the samples was measured using an impact tester (CEAST, IT-98).

(c) YI (yellowness index): The YI value was measured using a colorimeter (CM-3700D) according to ASTM D1925. A low YI value means less yellowing.

[Table 1]

Table 1 (continued)

As shown in Table 1, in the case of the polycarbonate resins of Examples 1 to 5 according to the present invention, compared with the polycarbonate resin of Comparative Example 1 (when prepared by a conventional interfacial polymerization method), the phosgene-based The amount of the material used is significantly reduced, the impact strength is 35Kg _f /cm ² or more, and the YI value is 2.4 or less, so it has excellent impact resistance and color. In addition, a high molecular weight polycarbonate resin having a viscosity average molecular weight of 20,000 or more can be obtained.

On the other hand, in the case of the polycarbonate resin of Comparative Example 1 (when prepared by a conventional interfacial polymerization method), the workability was poor since the amount of the toxic phosgene-based material used was very large. In the case of Comparative Examples 2 and 3 (conventional melt polymerization method), the color was poor due to the residual catalyst and thermal decomposition according to the high temperature reaction, and the YI value was 3.0 or more.

In addition, in the case of Comparative Example 4, the content of the ketone compound was relatively larger than that of the carbonic diester, so the viscosity average molecular weight of the polycarbonate resin was excessively increased, as a result, the processability decreased, and severe yellowing was observed, The YI value is 5.2. In the case of Comparative Example 5, the content of the ketone compound was relatively small compared with the carbonic diester, so that the reactivity was lowered, and the viscosity average molecular weight of the polycarbonate resin was less than 15,000, so that the high molecular weight polycarbonate could not be obtained. resin. In addition, the impact strength decreased and severe yellowing was observed, with a YI value of 4.2.

In the case of Comparative Example 6, since a large amount of the toxic phosgene-based compound was used, the workability was poor, the impact strength was also relatively low, and the color was poor, and the YI value was 3.0 or more. Due to the low content of isosorbide in the copolymer, it is also not suitable for use as an environmentally friendly material.

In the case of Comparative Example 7, as the isosorbide content increased, the toxic phosgene-based compound was used in a large amount, resulting in poor processability. High molecular weight polycarbonate resin could not be obtained due to reduced reactivity and viscosity average molecular weight of less than 15,000, impact strength was very poor, and severe yellowing was observed, with a YI value of 4.8.

Claims (9)

A polycarbonate resin comprising: a repeating unit derived from a carbonic acid diester component represented by the following formula 1; a repeating unit derived from a diol component represented by the following formula 2; and a ketone compound component represented by the following formula 3 A derived repeating unit wherein the polycarbonate resin comprises the carbonic diester component and the ketone component in a molar ratio of 1:0.02 to 1:0.2:

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms The aralkyl group of [Formula 2] HO-X-OH In formula 2, X is: a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight-chain alkylene group having 1 to 15 carbon atoms a branched-chain alkylene group having 3 to 15 carbon atoms; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohol, and the arylene group, straight Alkylene, branched and cyclic alkylene groups may be unsubstituted or substituted with halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryl groups, nitro groups or carboxyl groups, and

In Formula 3, R ₂ and R ₃ are each independently: a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; An aryl group of 6 to 50 carbon atoms; or an unsubstituted aryl group of 3 to 50 carbon atoms and having O or N, excluding that both R ₂ and R ₃ are halogen atoms. The polycarbonate resin according to claim 1, which has a viscosity average molecular weight of 10,000 to 70,000. A method of producing a polycarbonate resin comprising (1) producing by melt-polymerizing a repeating unit derived from a carbonic acid diester component represented by the following formula 1 and a repeating unit derived from a diol component represented by the following formula 2 Step of a hydroxyl-terminated polycarbonate oligomer having a unit structure represented by the following formula 4; and (2) by the prepared hydroxy-terminated polycarbonate oligomer and a ketone compound represented by the following formula 3 The step of preparing a polycarbonate resin by interfacial polymerization of components, wherein the reaction molar ratio of the carbonic acid diester component represented by the following formula 1 and the ketone compound component represented by the following formula 3 is 1:0.02 to 1:0.2 :

In Formula ₁ , each R is independently selected from unsubstituted or halogen-substituted alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryl groups having 7 to 25 carbon atoms The aralkyl group of [Formula 2] HO-X-OH In formula 2, X is a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; a straight-chain alkylene group having 1 to 15 carbon atoms ; a branched alkylene group having 3 to 15 carbon atoms; a cyclic alkylene group having 3 to 15 carbon atoms; or a divalent organic group derived from anhydrosugar alcohol, and the arylene, straight-chain Alkylene, branched alkylene and cyclic alkylene may be unsubstituted or substituted with halogen atoms, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, nitro or carboxy-substituted,

In formula 3, R ₂ and R ₃ are each independently a halogen atom; an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with O, N or Cl; an unsubstituted or Cl-substituted alkyl group having 6 an aryl group of to 50 carbon atoms; or an unsubstituted aryl group of 3 to 50 carbon atoms and having O or N, excluding that _both R and _R are halogen atoms, and

In Formula 4, X is as defined in Formula 2, and n represents an integer of 1 to 100. The method of claim 3, wherein the polycarbonate resin has a viscosity average molecular weight of 10,000 to 70,000. The method of claim 3, wherein the hydroxyl-terminated polycarbonate oligomer having the unit structure represented by Formula 4 has a viscosity average molecular weight of 1,000 to 20,000. The method of claim 3, wherein the melt polymerization of step (1) is carried out in the presence of a polymerization catalyst selected from the group consisting of alkali metal salt compounds, alkaline earth metal salt compounds, nitrogen-containing basic compounds or mixtures thereof. The method according to claim 3, wherein the melt polymerization of step (1) is performed by a step comprising: polymerizing a carbonic acid diester component represented by formula 1 and a diol component represented by formula 2 with polymerization The catalyst is mixed and the mixture is heated to 180°C to 240°C and a step of reacting the mixture at a temperature of 180° C. to 240° C. under a reduced pressure of 50 torr or less, and removing alcohol as a side reactant. The method according to claim 3, wherein the interfacial polymerization in step (2) is carried out under an interfacial reaction condition consisting of an aqueous alkali solution and an organic phase. A molded article comprising the polycarbonate resin according to claim 1 or 2.